CN109734843A - The preparation method and application of nano zero valence iron intercalated montmorillonite supported hydrogel - Google Patents
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Abstract
The present invention relates to a kind of preparation method and application of nano zero valence iron intercalated montmorillonite supported hydrogel, this method includes the preparation of the preparation of nano zero valence iron intercalated montmorillonite, the preparation of cellulose solution and nano zero valence iron intercalated montmorillonite supported hydrogel；Use cellulose aquagel for carrier, montmorillonite is dispersing agent, prepares iron based fiber element nanocomposite using sol-gel method；The nano zero valence iron intercalated montmorillonite supported hydrogel that this method is prepared is used to handle the waste water containing heavy metal.Compared with prior art, the present invention can effectively prevent the reunion of nano zero valence iron, improve the reactivity and utilization rate of nano zero valence iron, and good mobility can be contacted adequately with pollutant, quickly removal pollutant, provides significantly more efficient material and technical foundation for environmental pollution improvement.
Description
Technical field
The present invention relates to environment functional material fields, load water-setting more particularly, to a kind of nano zero valence iron intercalated montmorillonite
The preparation method and application of glue.
Background technique
Nano zero valence iron (nZVI) is with its superior absorption property, reduction activation, reaction rate and good environment phase
Capacitive and by the efficient improved materials as water pollution in-situ immobilization, in wastewater treatment, contaminated soil and groundwater remediation etc.
Field is widely used.However, there is also problems in practical applications by nZVI: (1) Zero-valent Iron itself is in air
In be easily oxidized, formed passivation layer and make active reduction.(2) nZVI is also easy to produce agglomeration due to itself existing magnetic, makes
Its specific surface area reduces, reaction rate decline, and reduces its mobile performance in water, is difficult to nZVI diffusion unevenly
It is completely attached to pollutant, to reduce utilization rate.(3) nZVI particle is small, and difficult recycling, is also easy to produce secondary dirt in water process
Dye.
In Chinese patent 201710786866.3, the preparation and its drop of a kind of calcium alginate cladded type Zero-valent Iron are provided
The method for solving dyestuff, preparation method is real using sodium alginate as matrix, obtains calcium alginate cladded type Zero-valent Iron gel ball, can have
Effect improves the stability of metal during the reaction, is easy to later period recycling and reusing.In Chinese patent 201210447511.9,
Disclose it is a kind of using montmorillonite as nano zero valence iron of carrier and preparation method thereof, zero in montmorillonite-loaded zero-valent iron composite material
Valence iron is between montmorillonite layer and space surface, and activity and stability are high and can be reduced nano zero valence iron polymerization.
It is of the existing technology the disadvantage is that: (1) in the method for Coated with Organic Matter modified Nano Zero-valent Iron, in nZVI particle table
Face forms clad, but clad is blocked up will lead to that mass transfer effect is poor, reduces nZVI to the degradation speed and ability of pollutant.
(2) nZVI dispersibility after cellular solid is loaded modified significantly improves, however in above-mentioned second patent, Zero-valent Iron exists
Between montmorillonite layer and space surface has load, but when nZVI particle is excessive, this can be easier in the nZVI that its surface has dispersed
Again reunite, cause area load uneven, be unfavorable for the generation of reaction, reduce its reactivity and utilization efficiency.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of nano zero valence irons to insert
The preparation method and application of layer montmorillonite load hydrogel.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel, comprising the following steps:
The preparation of nano zero valence iron intercalated montmorillonite
1) montmorillonite is added to FeCl3·6H2In O solution, Fe is obtained by being separated by solid-liquid separation, being dried after mixing3+
Intercalated montmorillonite；
2) by Fe in step 1)3+Intercalated montmorillonite is added in HCl solution and obtains souring soln, in the atmosphere of protective gas
By NaBH4Solution is added in the souring soln and carries out reduction reaction；Solution after reaction is separated by solid-liquid separation, ethanol washing,
The washing of anaerobic deionized water obtains nano zero valence iron intercalated montmorillonite after being dried；
The preparation of cellulose solution
Microcrystalline cellulose is dissolved in the mixed aqueous solution of NaOH and urea, is obtained after freezing processing, defrosting processing
Cellulose solution；
The preparation of nano zero valence iron intercalated montmorillonite supported hydrogel
The nano zero valence iron intercalated montmorillonite is added in the cellulose solution, acryloyl is sequentially added after stirring
Amine, ammonium persulfate, methylene-bisacrylamide obtain reaction solution, and reaction is carried out under constant temperature and forms gel, by the gel
Freeze-drying, obtains the nano zero valence iron intercalated montmorillonite supported hydrogel.
The montmorillonite is the ca-montmorillonite after purification process, and partial size is 1~3 μm；The FeCl3·6H2O solution
Concentration be 0.06~0.15mol/L；Fe3+The content of exchangeability Fe is the 4 of montmorillonite cation exchange capacity (CEC) in intercalated montmorillonite
~10 times, specific relationship are as follows: montmorillonite quality × montmorillonite cation exchange capacity (CEC) × multiple=iron cation valence number
The mole of × iron containing compounds.
In the reduction reaction, Fe3+Intercalated montmorillonite: HCl:NaBH4Proportion be 3g:(50~100) mL:(100~
200)mL；The concentration of the HCl solution is 0.5~1mol/L；The NaBH4The concentration of solution is 0.05~0.1mol/L.
The concentration of the HCl solution is 1mol/L；The NaBH4The concentration of solution is 0.1mol/L.
The concentration of NaOH is 0.02~0.032g/ml in the mixed aqueous solution of the NaOH and urea, and the concentration of urea is
0.04~0.06g/ml；The additive amount of microcrystalline cellulose is 0.02~0.04g/ml.
The concentration of NaOH is 0.028g/ml in the mixed aqueous solution of the NaOH and urea, and the concentration of urea is 0.048g/
ml；The additive amount of microcrystalline cellulose is 0.05g/ml.
In the preparation step of the nano zero valence iron intercalated montmorillonite supported hydrogel, the nano zero valence iron intercalation covers de-
Soil: microcrystalline cellulose: acrylamide: ammonium persulfate: the mass ratio of methylene-bisacrylamide be 20~30:5~10:16~
20:1~5:1~3；Constant temperature corresponding temperature is 50~80 DEG C；Reaction time is 3~6h.
In the preparation step of the nano zero valence iron intercalated montmorillonite, the drying process in step 1) and step 2) is specially
Vacuum condition, temperature are 30~50 DEG C, dry 10~15h, dry 12h at preferably 60 DEG C；
In the preparation step of the cellulose solution, the time of freezing processing is 10~15h, and cryogenic temperature is -70~-40
DEG C, 12h is freezed at preferably -60 DEG C；
In the preparation step of the nano zero valence iron intercalated montmorillonite supported hydrogel, the temperature of the gel refrigeration drying
It is -70~-40 DEG C, preferably -60 DEG C freezing 12h.
The present invention also provides a kind of method for handling waste water, the nano zero valence iron intercalation which is obtained covers de-
It, will be in waste water to after reaction be separated by solid-liquid separation waste water in native waste water of the supported hydrogel investment containing heavy metal ion
Heavy metal ions removal.
For the present invention using cellulose aquagel as carrier, montmorillonite is dispersing agent, and there is high degree of dispersion and high reaction to live for preparation
The nano zero valence iron of property.The preparation method can effectively prevent the reunion of nano zero valence iron, and the reaction for improving nano zero valence iron is living
Property, and there is good mobility, it can adequately be contacted with pollutant, quickly remove pollutant.
It is prepared by the present invention that dirt in various waste water is being removed with nano zero valence iron intercalated montmorillonite supported hydrogel material
Object is contaminated, especially has significant removal effect to the removal of the heavy metal in water.Zero-valent Iron intercalated montmorillonite obtained is born
It carries hydrogel to direct plunge into waste water, the absorption and reduction using material to pollutant reach the quick removal of pollutant.
In order to obtain the preferable nano zero valence iron intercalated montmorillonite supported hydrogel material of effect, key is NaBH4's
Mole is the FeCl of addition3·6H23~5 times or so of O amount, if NaBH4Additive amount it is excessive or very few, then Fe3+Intercalation covers
NaBH in de- soil4Surplus cannot excessively be removed or iron ion can not be completely reduced as Zero-valent Iron, to influence
The preparation of material influences experimental result.
Compared with prior art, the invention has the following advantages that
One, the present invention is to stabilize carrier with hydrogel, and steric hindrance caused by tridimensional network not only can be right
NZVI plays stabilization, also provides channel for the mass transport process in reaction, comes into full contact with reactant with nZVI, improves reaction
Rate.
Two, the present invention constructs two-dimentional " nanometer microreactor " between cheating engaging layer, utilizes the interlayer confinement effect of montmorillonite
The other Zero-valent Iron of fabricated in situ Subnano-class, to effectively improve the reactivity and service life of material.
Three, the present invention is by being combined two big structure characteristic advantage of montmorillonite and hydrogel, using montmorillonite as inorganic
Crosslinking agent and dispersing agent are combined in hydrogel three-dimensional network, effectively improve the degree of order and dispersibility of nZVI, this is in fact
Good basis has been established in border application.
Detailed description of the invention
Fig. 1 is the SEM photograph of zero-valent iron material；
Fig. 2 is the SEM photograph that the present invention prepares material；
Fig. 3 is zero-valent iron material and present invention preparation experimental result of the material processing containing hexavalent chromium wastewater.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1
The montmorillonite (cation exchange capacity (CEC) 90cmol/kg, partial size are 1 μm) of 1g is added to 20mL 0.06mol/L's
FeCl3·6H2O solution is centrifuged again after shaking up mixing, obtains Fe after being dried in vacuo 10h at 30 DEG C3+Intercalated montmorillonite particle.
Then Fe 1g being prepared3+Intercalated montmorillonite is added in the HCl of 50mL 0.5mol/L, in N2Under protection, quickly by 96mL
The NaBH of 0.05mol/L4Persistently stirring 1h in the solution that solution is added after acidification makes fully reacting.It is centrifuged after reaction, so
It is washed 3 times with dehydrated alcohol, then is rinsed for several times with anaerobic deionized water afterwards, is finally placed in a vacuum drying oven at 60 DEG C dry
12h obtains the nano zero valence iron intercalated montmorillonite of black.The urea of the NaOH and 10g of 5g is taken to dissolve constant volume in 250mL capacity
Bottle, is denoted as NaOH/ urea liquid.0.5g microcrystalline cellulose is dissolved in 10mL NaOH/ urea liquid, is freezed at -70 DEG C
It thaws after 10h, obtains cellulose solution.Then the above-mentioned nano zero valence iron intercalated montmorillonite of 2g is added in cellulose solution, is stirred
1.6g acrylamide, 0.1g ammonium persulfate, 0.1g methylene-bisacrylamide are sequentially added after mixing uniformly, and stirring is to being completely dissolved
Afterwards, it is placed in thermostat water bath and reacts 3h at 50 DEG C, until gel stability is dry.Finally it is freeze-dried at -70 DEG C
10h obtains Zero-valent Iron intercalated montmorillonite supported hydrogel.
Embodiment 2
The montmorillonite (cation exchange capacity (CEC) 90cmol/kg, partial size are 2 μm) of 1g is added to 20mL 0.09mol/L's
FeCl3·6H2O solution is centrifuged again after shaking up mixing, and 11h is dried in vacuo at 35 DEG C and obtains Fe3+Intercalated montmorillonite particle.So
The Fe that 1g is prepared afterwards3+Intercalated montmorillonite is added in the HCl of 60mL 0.5mol/L, in N2Under protection, quickly by 144mL
The NaBH of 0.05mol/L4Persistently stirring 1h in the solution that solution is added after acidification makes fully reacting.It is centrifuged after reaction, so
It is washed 3 times with dehydrated alcohol, then is rinsed for several times with anaerobic deionized water afterwards, is finally placed in a vacuum drying oven at 60 DEG C dry
12h obtains the nano zero valence iron intercalated montmorillonite of black.The urea of the NaOH and 11g of 6g is taken to dissolve constant volume in 250mL capacity
Bottle, is denoted as NaOH/ urea liquid.0.8g microcrystalline cellulose is dissolved in 16mL NaOH/ urea liquid, is freezed at -50 DEG C
It thaws after 11h, obtains cellulose solution.Then the above-mentioned nano zero valence iron intercalated montmorillonite of 2g is added in cellulose solution, is stirred
1.6g acrylamide, 0.2g ammonium persulfate, 0.2g methylene-bisacrylamide are sequentially added after mixing uniformly, and stirring is to being completely dissolved
Afterwards, it is placed in thermostat water bath and reacts 5h at 70 DEG C, until gel stability is dry.It finally is freeze-dried 11h at -50 DEG C,
Obtain Zero-valent Iron intercalated montmorillonite supported hydrogel.
Embodiment 3
The montmorillonite (cation exchange capacity (CEC) 90cmol/kg, partial size are 3 μm) of 1g is added to 20mL 0.12mol/L's
FeCl3·6H2O solution is centrifuged again after shaking up mixing, obtains Fe after being dried in vacuo 12h at 40 DEG C3+Intercalated montmorillonite particle.
Then Fe 1g being prepared3+Intercalated montmorillonite is added in the HCl of 50mL 1mol/L, in N2Under protection, quickly by 96mL
The NaBH of 0.1mol/L4Persistently stirring 1h in the solution that solution is added after acidification makes fully reacting.It is centrifuged after reaction, then
It is washed 3 times with dehydrated alcohol, then is rinsed for several times with anaerobic deionized water, is finally placed in a vacuum drying oven at 60 DEG C dry
12h obtains the nano zero valence iron intercalated montmorillonite of black.The urea of the NaOH and 12g of 7g is taken to dissolve constant volume in 250mL capacity
Bottle, is denoted as NaOH/ urea liquid.0.6g microcrystalline cellulose is dissolved in 12mL NaOH/ urea liquid, is freezed at -60 DEG C
It thaws after 12h, obtains cellulose solution.Then the above-mentioned nano zero valence iron intercalated montmorillonite of 3g is added in cellulose solution, is stirred
1.8g acrylamide, 0.3g ammonium persulfate, 0.1g methylene-bisacrylamide are sequentially added after mixing uniformly, and stirring is to being completely dissolved
Afterwards, it is placed in thermostat water bath and reacts 4h at 60 DEG C, until gel stability is dry.Finally it is freeze-dried at -60 DEG C
12h obtains Zero-valent Iron intercalated montmorillonite supported hydrogel.
Embodiment 4
The montmorillonite (cation exchange capacity (CEC) 90cmol/kg, partial size are 3 μm) of 1g is added to 20mL 0.15mol/L's
FeCl3·6H2O solution is centrifuged again after shaking up mixing, obtains Fe after being dried in vacuo 15h at 50 DEG C3+Intercalated montmorillonite particle.
Then Fe 1g being prepared3+Intercalated montmorillonite is added in the HCl of 100mL 1mol/L, in N2Under protection, quickly by 120mL
The NaBH of 0.1mol/L4Persistently stirring 1h in the solution that solution is added after acidification makes fully reacting.It is centrifuged after reaction, then
It is washed 3 times with dehydrated alcohol, then is rinsed for several times with anaerobic deionized water, is finally placed in a vacuum drying oven at 60 DEG C dry
12h obtains the nano zero valence iron intercalated montmorillonite of black.The urea of the NaOH and 15g of 8g is taken to dissolve constant volume in 250mL capacity
Bottle, is denoted as NaOH/ urea liquid.1g microcrystalline cellulose is dissolved in 20mL NaOH/ urea liquid, freezes 15h at -40 DEG C
After thaw, obtain cellulose solution.Then the above-mentioned nano zero valence iron intercalated montmorillonite of 3g is added in cellulose solution, stirring is equal
2g acrylamide, 0.5g ammonium persulfate, 0.3g methylene-bisacrylamide are sequentially added after even, are stirred to after being completely dissolved, are put
6h is reacted at 80 DEG C in thermostat water bath, until gel stability is dry.It finally is freeze-dried 15h at -40 DEG C, obtains zero
Valence iron intercalated montmorillonite supported hydrogel.
The nano zero valence iron intercalated montmorillonite water load that current zero-valent iron material and the present embodiment are prepared
The SEM figure of gel rubber material compares, discovery nano zero-valence iron particle be substantially in it is spherical, partial size is smaller and large specific surface area, empty
Between it is upper be dendritic structure, reunite integral, as shown in Figure 1；And it can see in the SEM figure for the material that the present invention is prepared
Nano iron particles are uniformly dispersed in without apparent agglomeration in cheating engaging layer spacing, as shown in Fig. 2, this illustrates nanometer zero
Valence iron intercalated montmorillonite supported hydrogel material, can effectively overcome the agglomeration of nano zero valence iron, improve its point
Dissipate property and stability.
Four kinds of Zero-valent Iron intercalated montmorillonite supported hydrogel new materials processing that Examples 1 to 4 is prepared is containing chromium
Waste water, wherein the concentration of Cr VI is 20mg/L, and reaction temperature is 30 DEG C, reaction time 3h.Specific process parameter and removal
Rate is as shown in table 1.
The experimental data of Zero-valent Iron intercalated montmorillonite supported hydrogel new material processing waste water in 1 Examples 1 to 4 of table
Further by Zero-valent Iron intercalated montmorillonite supported hydrogel new material prepared by the present invention and nano zero-valence iron material
Material processing effect containing hexavalent chromium wastewater compares, and obtains Cr (VI) removal rate and reaction time relation function curve graph, such as Fig. 3
It is shown, find Cr (VI) removal rate as the reaction time is gradually increased and finally tends towards stability, the wherein Cr of nano zero valence iron
(VI) removal rate is finally reached 45.60%, and Cr (VI) removal rate of nano zero valence iron intercalated montmorillonite supported hydrogel is final
Reach 99.13%.In contrast, the reaction of nano iron particles is relatively slower and removal efficiency is covered far below nano zero valence iron intercalation
De- soil supported hydrogel material.
Embodiment 5
The montmorillonite (cation exchange capacity (CEC) 90cmol/kg, partial size are 3 μm) of 1g is added to 20mL 0.15mol/L's
FeCl3·6H2O solution is centrifuged again after shaking up mixing, obtains Fe after being dried in vacuo 15h at 50 DEG C3+Intercalated montmorillonite particle.
Then Fe 1g being prepared3+Intercalated montmorillonite is added in the HCl of 100mL 1mol/L, in N2Under protection, quickly by 200mL
The NaBH of 0.05mol/L4Persistently stirring 1h in the solution that solution is added after acidification makes fully reacting.It is centrifuged after reaction, so
It is washed 3 times with dehydrated alcohol, then is rinsed for several times with anaerobic deionized water afterwards, is finally placed in a vacuum drying oven at 60 DEG C dry
12h obtains the nano zero valence iron intercalated montmorillonite of black.The urea of the NaOH and 15g of 8g is taken to dissolve constant volume in 250mL capacity
Bottle, is denoted as NaOH/ urea liquid.1g microcrystalline cellulose is dissolved in 20mL NaOH/ urea liquid, freezes 15h at -40 DEG C
After thaw, obtain cellulose solution.Then the above-mentioned nano zero valence iron intercalated montmorillonite of 3g is added in cellulose solution, stirring is equal
2g acrylamide, 0.5g ammonium persulfate, 0.3g methylene-bisacrylamide are sequentially added after even, are stirred to after being completely dissolved, are put
6h is reacted at 80 DEG C in thermostat water bath, until gel stability is dry.It finally is freeze-dried 15h at -40 DEG C, obtains zero
Valence iron intercalated montmorillonite supported hydrogel.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel, which comprises the following steps:
The preparation of nano zero valence iron intercalated montmorillonite
1) montmorillonite is added to FeCl3·6H2In O solution, Fe is obtained by being separated by solid-liquid separation, being dried after mixing3+Intercalation covers
De- soil；
2) by Fe in step 1)3+Intercalated montmorillonite is added in HCl solution and obtains souring soln, will in the atmosphere of protective gas
NaBH4Solution is added in the souring soln and carries out reduction reaction；Solution after reaction is separated by solid-liquid separation, ethanol washing, nothing
The washing of oxygen deionized water obtains nano zero valence iron intercalated montmorillonite after being dried；
The preparation of cellulose solution
Microcrystalline cellulose is dissolved in the mixed aqueous solution of NaOH and urea, obtains fiber after freezing processing, defrosting processing
Plain solution；
The preparation of nano zero valence iron intercalated montmorillonite supported hydrogel
The nano zero valence iron intercalated montmorillonite is added in the cellulose solution, acrylamide, mistake are sequentially added after stirring
Ammonium sulfate, methylene-bisacrylamide obtain reaction solution, and reaction is carried out under constant temperature and forms gel, the gel are freezed dry
It is dry, obtain the nano zero valence iron intercalated montmorillonite supported hydrogel.
2. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 1, feature
It is, the montmorillonite is the ca-montmorillonite after purification process, and partial size is 1~3 μm；The FeCl3·6H2O solution it is dense
Degree is 0.06~0.15mol/L；Fe3+The content of exchangeability Fe is the 4~10 of montmorillonite cation exchange capacity (CEC) in intercalated montmorillonite
Times.
3. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 1, feature
It is, in the reduction reaction, Fe3+Intercalated montmorillonite: HCl:NaBH4Proportion be 1g:(50~100) mL:(100~200)
mL；The concentration of the HCl solution is 0.5~1mol/L；The NaBH4The concentration of solution is 0.05~0.1mol/L.
4. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 3, feature
It is, the concentration of the HCl solution is 1mol/L；The NaBH4The concentration of solution is 0.1mol/L.
5. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 1, feature
It is, the concentration of NaOH is 0.02~0.032g/ml in the mixed aqueous solution of the NaOH and urea, and the concentration of urea is 0.04
~0.06g/ml；The additive amount of microcrystalline cellulose is 0.02~0.04g/ml.
6. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 5, feature
It is, the concentration of NaOH is 0.028g/ml in the mixed aqueous solution of the NaOH and urea, and the concentration of urea is 0.048g/ml；
The additive amount of microcrystalline cellulose is 0.05g/ml.
7. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 1, feature
It is, in the preparation step of the nano zero valence iron intercalated montmorillonite supported hydrogel, the nano zero valence iron intercalated montmorillonite:
Microcrystalline cellulose: acrylamide: ammonium persulfate: the mass ratio of methylene-bisacrylamide is 20~30:5~10:16~20:1
~5:1~3；Constant temperature corresponding temperature is 50~80 DEG C；Reaction time is 3~6h.
8. a kind of preparation method of nano zero valence iron intercalated montmorillonite supported hydrogel according to claim 1, feature
It is,
In the preparation step of the nano zero valence iron intercalated montmorillonite, the drying process in step 1) and step 2) is specially vacuum
Condition, temperature are 30~50 DEG C, dry 10~15h, dry 12h at preferably 60 DEG C；Protective gas is nitrogen；
In the preparation step of the cellulose solution, the time of freezing processing is 10~15h, and cryogenic temperature is -70~-40 DEG C,
12h is freezed at preferably -60 DEG C；
In the preparation step of the nano zero valence iron intercalated montmorillonite supported hydrogel, the temperature of the gel refrigeration drying is-
70~-40 DEG C, preferably -60 DEG C.
9. the application for the nano zero valence iron intercalated montmorillonite supported hydrogel that preparation method as described in claim 1 obtains, will
In waste water of the nano zero valence iron intercalated montmorillonite supported hydrogel investment containing heavy metal ion that the preparation method obtains, band reaction
After waste water is separated by solid-liquid separation, by the heavy metal ions removal in waste water.
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| CN111531183A (en) * | 2020-05-11 | 2020-08-14 | 南昌航空大学 | Organically modified biotite loaded superfine nano zero-valent zinc suitable for degradation of heavy non-aqueous phase halogenated pollutants and preparation method thereof |
| CN113683179A (en) * | 2021-09-10 | 2021-11-23 | 华南农业大学 | Method for degrading bisphenol compounds in water body based on magnetic lignin hydrogel activated persulfate |
| CN113751492A (en) * | 2021-09-10 | 2021-12-07 | 华南农业大学 | Method for repairing organic contaminated soil by using magnetic lignin hydrogel to activate persulfate |
| CN114479165A (en) * | 2022-02-28 | 2022-05-13 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN116371381A (en) * | 2023-04-28 | 2023-07-04 | 浙江大学 | Pollutant response type nano zero-valent iron composite functional material and application thereof |
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| CN113683179A (en) * | 2021-09-10 | 2021-11-23 | 华南农业大学 | Method for degrading bisphenol compounds in water body based on magnetic lignin hydrogel activated persulfate |
| CN113751492A (en) * | 2021-09-10 | 2021-12-07 | 华南农业大学 | Method for repairing organic contaminated soil by using magnetic lignin hydrogel to activate persulfate |
| CN113683179B (en) * | 2021-09-10 | 2022-11-29 | 华南农业大学 | Method for degrading bisphenol compounds in water body based on magnetic lignin hydrogel activated persulfate |
| CN114479165A (en) * | 2022-02-28 | 2022-05-13 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN114479165B (en) * | 2022-02-28 | 2023-10-24 | 苏州大学 | Method for preparing composite aerogel from montmorillonite microspheres and regenerated cellulose |
| CN116371381A (en) * | 2023-04-28 | 2023-07-04 | 浙江大学 | Pollutant response type nano zero-valent iron composite functional material and application thereof |
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